Description and evaluation of a model of deposition velocities for routine estimates of dry deposition over North America. Part II: review of past measurements and model results

Numerical sensitivity tests and four months of complete model runs have been conducted for the Routine Deposition Model (RDM). The influence of individual model inputs on dry deposition velocity as a function of land-use category (LUC) and pollutant (SO₂, O₃, SO²⁻₄ and HNO₃) were examined over a realistic range of values for solar radiation, stability and wind speed. Spatial and temporal variations in RDM deposition velocity (V_d) during June – September 1996 time period generated using meteorological input from a mesoscale model run at 35 km resolution over north-eastern North America were also examined. Comparison of RDM V_d values to a variety of measurements of dry deposition velocities of SO₂, O₃, SO²⁻₄ and NHO₃ that have been reported in the literature demonstrated that RDM produces realistic results. Over northeastern NA RDM monthly averaged dry deposition velocities for SO₂ vary from 0.2 to 3.0 cm s⁻¹ with the highest deposition velocities over water surfaces. For O₃, the monthly averaged dry deposition velocities are from 0.05 to 1.0 cm s⁻¹ with the lowest values over water surfaces and the highest over forested areas. For HNO₃, the monthly averaged dry deposition velocities have the range of 0.5 to 6 cm s⁻¹, with the highest values for forested areas. For SO²⁻₄, they range from 0.05–1.5 cm s⁻¹, with the lowest values over water and the highest over forest. The monthly averaged dry deposition velocities for SO₂ and O₃ are higher in the growing season compared to the fall, but this behaviour is not apparent for HNO₃ and sulphate. In the daytime, the hourly averaged dry deposition velocities for SO₂, O₃, SO²⁻₄ and HNO₃ are higher than that in the nighttime over most of the vegetated area. The diurnal variation is most evident for surfaces with large values for leaf area index (LAI), such as forests. Based on the results presented in this paper, it is concluded that RDM V_d values can be combined with measured air concentrations over hourly, daily or weekly periods to determine dry deposition amounts and with wet deposition measurements to provide seasonal estimates of total deposition and estimates of the relative importance of dry deposition.     

A DFT study of the reactions of O3 with Hg° or Br

In the mid 1980s the study of ozone reactivity gained a significant interest with the discoveries of the stratospheric ozone hole (Farman et al., 1985) and of the ozone depletion events in the polar boundary layer (Oltmans et al., 1989). In the stratosphere, the mechanism involves heterogeneous reactions on polar stratospheric clouds that lead to chlorine activation (Solomon et al., 1986). In contrast, tropospheric ozone depletion occurring during polar springtime rather involves reactive bromine species. They are released during a series of photochemical and heterogeneous reactions often called the bromine explosion (see the review of Simpson et al., 2007). In this reaction sequence, an essential step is the generation of photolyzable Br₂, the precursor of two Br atoms, via the multiphasic reaction (1):

(1)

HOBr + Br⁻ + H⁺ → H₂O + Br₂

The production of reactive HOBr could occur with the oxidation of BrO by HO₂.     

The influence of forest fires on CO, HCN, C2H6, and C2H2 over northern Japan measured by infrared solar spectroscopy

Total column abundances of CO, HCN, C₂H₆, and C₂H₂ have been retrieved from infrared solar spectra observed at Moshiri (44.4°N) and Rikubetsu (43.5°N) in northern Japan from 1997 to 2005. The spectra were recorded with high spectral resolution ground-based Fourier transform infrared (FTIR) spectrometers and total column abundances were calculated by SFIT1 version 1.09e. Deviations of these species relative to their seasonal mean values (ΔCO, ΔHCN, ΔC₂H₆, and ΔC₂H₂) were derived, which showed short-time enhancements in 1998, 2002, and 2003. Good correlations among ΔCO, ΔHCN, ΔC₂H₆, and ΔC₂H₂ in a few months of each year were seen. Since the number of forest fires in Siberia had large enhancements in 1998, 2002, and 2003, trajectory analyses were performed in order to assess the influence of forest fires and it was confirmed that air masses passing over the location of burning points in Siberia reached Moshiri and Rikubetsu. This paper shows that enhancements of these species were driven by biomass burning in Siberia.     

Simple model for estimating dry deposition velocity of ozone and its destruction in a polluted nocturnal boundary layer

Determining the destructions of both ozone and odd oxygen, O_x, in the nocturnal boundary layer (NBL) is important to evaluate the regional ozone budget and overnight ozone accumulation. This work develops a simple method to determine the dry deposition velocity of ozone and its destruction at a polluted nocturnal boundary layer. The destruction of O_x can also be determined simultaneously. The method is based on O₃ and NO₂ profiles and their surface measurements. Linkages between the dry deposition velocities of O₃ and NO₂ and between the dry deposition loss of O_x and its chemical loss are constructed and used. Field measurements are made at an agricultural site to demonstrate the application of the model. The model estimated nocturnal O₃ dry deposition velocities from 0.13 to 0.19 cm s^?1, very close to those previously obtained for similar land types. Additionally, dry deposition and chemical reactions account for 60 and 40% of the overall nocturnal ozone loss, respectively; ozone dry deposition accounts for 50% of the overall nocturnal loss of O_x, dry deposition of NO₂ accounts for another 20%, and chemical reactions account for the remaining 30%. The proposed method enables the use of measurements made in typical ozone field studies to evaluate various nocturnal destructions of O₃ and O_x in a polluted environment.     

Assessment of traffic-related air pollution in the urban streets before and during the 2008 Beijing Olympic Games traffic control period

In order to investigate the air quality and the abatement of traffic-related pollution during the 2008 Olympic Games, we select 12 avenues in the urban area of Beijing to calculate the concentrations of PM₁₀, CO, NO₂ and O₃ before and during the Olympic traffic controlling days, with the OSPM model.Through comparing the modeled results with the measurement results on a representative street, the OSPM model is validated as sufficient to predict the average concentrations of these pollutants at street level, and also reflects their daily variations well, i.e. CO presents the similar double peaks as the traffic flow, PM₁₀ concentration is influenced by other sources. Meanwhile, the model predicts O₃ to stay less during the daytime and ascend in the night, just opposite to NO₂, which reveals the impact of photochemical reactions. In addition, the predicted concentrations on the windward side often exceed the leeward side, indicating the impact of the special street shape, as well as the wind.The comparison between the predicted street concentrations before and during the Olympic traffic control period shows that the overall on-road air quality was improved effectively, due to the 32.3% traffic flow reduction. The concentrations of PM₁₀, CO and NO₂ have reduced from 142.6 μg m⁻³, 3.02 mg m⁻³ and 118.7 μg m⁻³ to 102.0 μg m⁻³, 2.43 mg m⁻³ and 104.1 μg m⁻³. However, the different pollutants show diverse changes after the traffic control. PM₁₀ decreases most, and the reduction effect focusing on the first half-day even clears the morning peak, whereas CO and NO₂ have even reductions to minify the daily fluctuations on the whole. Opposite to the other pollutants, ozone shows an increase of concentration. The average reduction rate of PM₁₀, CO, NO₂ and O₃ are respectively 28%, 19.3%, 12.3% and −25.2%. Furthermore, the streets in east, west, south and north areas present different air quality improvements, probably induced by the varied background pollution in different regions around Beijing, along with the impact of wind force. This finding suggests the pollution control in the surrounding regions, not only in the urban area.     

A new approach to quantify the degradation kinetics of linuron with UV, ozonation and UV/O3 processes

The degradation of linuron, one of phenylurea herbicides, was investigated for its reaction kinetics by different treatment processes including ultraviolet irradiation (UV), ozonation (O₃), and UV/O₃. The decay rate of linuron by UV/O₃ process was found to be around 3.5 times and 2.5 times faster than sole-UV and ozone-alone, respectively. Experimental results also indicate overall rate constants increased exponentially with pH above 9.0 while the increase of rate constants with pH below 9 is insignificant in O₃ system. All dominant parameters involved in the three processes were determined in the assistant of proposed linear models in this study. The approach was found useful in predicting the process performances through the quantification of quantum yield (rate constant for the formation of free radical HOO⁻ from ozone decomposition at high pH), rate constant of linuron with ozone (k_O3,LNR), rate constant of linuron with hydroxyl radical (k_OH,LNR), and α (the ratio of the production rate of OH and the decay rate of ozone in UV/O₃ system).     

Changes in biomass activity and characteristics of activated sludge exposed to low ozone dose

In this paper, the response mechanism of activated sludge exposed to low-dose ozone at less than 20 mg O₃ g⁻¹ total suspended solids (TSS) was studied by analyzing the changes in sludge activity and the evolution of C, N, P and metals from sludge following ozonation. The intracellular ATP concentration was not affected at less than 5 mg O₃ g⁻¹ TSS and thereafter decreased rapidly to around 60% when the ozone dose increased to 20 mg O₃ g⁻¹ TSS. Similarly, the efficiency of sludge solubilization initially changed a little and then increased rapidly to around 30% at an ozone dose of 20 mg O₃ g⁻¹ TSS. However, the activities of superoxide dismutase and protease decreased immediately upon exposure to ozone. These findings indicate that ozone firstly destroys the floc, leading to the disruption of the compact aggregates, which does not affect cells viability but induces a decrease in enzyme activities. Ozone then attacks the bacterial cells of the sludge, causing a decrease in cells viability. During ozonation, the content of carbon, nitrogen and phosphorus in the sludge matrix decreased, while the content of these elements in the micro-solids and supernatant gradually increased. Most of the released metals from the sludge matrix were found in the micro-solids.     

Photochemical production of ozone and control strategy for Southern Taiwan

An observation-based method (OBM) is developed to evaluate the ozone (O₃) production efficiency (O₃ molecules produced per NO_x molecule consumed) and O₃ production rate (P(O₃)) during a field campaign in southern Taiwan. The method can also provide an estimate of the concentration of OH. A key step in the method is to use observed concentrations of two aromatic hydrocarbons, namely ethylbenzene and m,p-xylene, to estimate the degree of photochemical processing and amounts of photochemically consumed NO_x and NMHCs by OH. In addition, total oxidant (O₃+NO₂) instead of O₃ itself turns out to be very useful for representing ozone production in the OBM approach. The average O₃ production efficiency during the field campaign in Fall (2003) is found to be about 10.2±3.9. The relationship of P(O₃) with NO_x is examined and compared with a one-dimensional (1D) photochemical model. Values of P(O₃) derived from the OBM are slightly lower than those calculated in the 1D model. However, OH concentrations estimated by the OBM are about a factor of 2 lower than the 1D model. Fresh emissions, which affect the degree of photochemical processing appear to be a major cause of the underestimate. We have developed a three-dimensional (3D) OBM O₃ production diagram that resembles the EKMA ozone isopleth diagram to study the relationship of the total oxidant versus O₃ precursors. The 3D OBM O₃ production diagram suggests that reducing emissions of NMHCs are more effective in controlling O₃ than reducing NO_x. However, significant uncertainties remain in the OBM, and considerable more work is required to minimize these uncertainties before a definitive control strategy can be reached. The observation-based approach provides a good alternative to measuring peroxy radicals for evaluating the production of O₃ and formulating O₃ control strategy in urban and suburban environments.     

Estimates of AOT ozone indices from time-integrated ozone data and hourly air temperature measurements in southwest Sweden

Surface ozone concentration and surface air temperature was measured hourly at three coastal sites, four low elevation inland sites and two high elevation inland sites in southwestern Sweden. Diurnal ozone concentration range (DOR) and diurnal temperature range (DTR) were strongly correlated, both spatially and temporally, most likely because both depended on atmospheric stability. Accumulated ozone exposure above a threshold concentration of x nmol mol⁻¹ (AOTx) was estimated from time-integrated ozone concentration (as from diffusive sampling) and measures of ozone concentration variability. Two methods both estimated 24-h AOTx with high accuracy (modelling efficiencies >90% for x ≤ 40 nmol mol⁻¹). Daytime (08:00–20:00) AOTx could not be equally well estimated. Estimates were better for lower AOT thresholds. Diffusive ozone concentration sampling, combined with hourly temperature monitoring, could be a valuable complement to ozone concentration monitoring with continuous instruments.     

Description and evaluation of a model of deposition velocities for routine estimates of air pollutant dry deposition over North America.: Part I: model development

This paper describes the development of a detailed dry deposition model for routine computation of dry deposition velocities of SO₂, O₃, HNO₃ and fine particle SO₄²⁻ across much of North America. Four different dry deposition/surface exchange sub-models have been combined with the current Canadian weather forecast model (Global Environmental Multiscale model) with a 3 h time resolution and a horizontal spatial resolution of 35 km. The present model uses the US Geological Survey North American Land Cover Characteristics data to obtain fourteen different land use and five seasonal categories. The four sub-models used are a multi-layer model for gaseous species over taller canopy land-use types, a big-leaf model for gaseous species over lower canopies (including bare soil and water) and for HNO₃ under all surface types and, two different models for SO₄²⁻, one for tall canopies and the other for short canopies. All necessary parameters for each sub-model, chemical species, land-use and seasonal categories have been selected from available data libraries or from the values reported in the literature. The purpose for developing this model (referred to as the Routine Deposition Model (RDM)), when coupled with air concentration data, is to provide estimates of seasonal dry deposition, which can be combined with wet deposition to produce total deposition estimates. Model theory is discussed in this paper and model sensitivity tests and results will be presented in a companion paper.     

A study of the atmospheric reaction of CH3S with O3 as a function of temperature

The atmospheric reaction of the methylthiyl radical (CH₃S) with O₃ was investigated as a function of temperature (259–381 K), in the pressure range of 25–300 Torr, using the technique of laser photolysis/laser-induced fluorescence. The resulting Arrhenius expression, with an uncertainty of ±2σ, was k₁(T=259–381 K)=(1.02±0.30)×10⁻¹² exp[(432±77) K/T] cm³ molecule⁻¹ s⁻¹. The obtained rate constant k₁ was independent of pressure over the limited range employed. Our results are compared with the previous studies carried out, at single temperature and as a function of temperature, by different techniques.     

The influence of south foehn on the ozone mixing ratios at the high alpine site Arosa

Within 2 years of trace gas measurements performed at Arosa (Switzerland, 2030 m above sea level), enhanced ozone mixing ratios were observed during south foehn events during summer and spring (5–10 ppb above the median value). The enhancements can be traced back to ozone produced in the strongly industrialized Po basin as confirmed by various analyses. Backward trajectories clearly show advection from this region during foehn. NO_y versus O₃ correlation and comparison of O₃ mixing ratios between Arosa and Mt. Cimone (Italy, 2165 m asl) suggest that ozone is the result of recent photochemical production (+5.6 ppb on average), either directly formed during the transport or via mixing of air processed in the Po basin boundary layer. The absence of a correlation between air parcel residence times over Europe and ozone mixing ratios at Arosa during foehn events is in contrast to a previous analysis, which suggested such correlation without reference to the origin of the air. In the case of south foehn, the continental scale influence of pollutants emission on ozone at Arosa appears to be far less important than the direct influence of the Po basin emissions. In contrast, winter time displays a different situation, with mean ozone reductions of about 4 ppb for air parcels passing the Po basin, probably caused by mixing with ozone-poor air from the Po basin boundary layer.     

Monoterpene emissions and carbonyl compound air concentrations during the blooming period of rape (Brassica napus)

An increasing percentage of agricultural land in Germany is used for oil seed plants. Hence, rape has become an important agricultural plant (in Saxony 1998: 12% of the farmland) in the recent years. During flowering of rape along with intensive radiation and high temperatures, a higher production and emission of biogenic VOC was observed. The emissions of terpenes were determined and more importantly, high concentrations of organic carbonyl compounds were observed during this field experiment. All measurements of interest have been carried out during two selected days with optimal weather conditions. It is found that the origin or the mechanism of formation of different group of compounds had strong influence on the day to day variation of their concentrations. The emission flux of terpenes from flowering rape plants was determined to be 16–32 μg h⁻¹ m⁻² (30–60 ng h⁻¹ per g dry plant––540–1080 ng h⁻¹ per plant), in total. Limonene, α-thujene and sabinene were the most important compounds (about 60% of total terpenes). For limonene and sabinene reference emission rates (M_S) and temperature coefficients were determined: β_limonene=0.108 K⁻¹ and M_S=14.57 μg h⁻¹ m⁻²; β_sabinene=0.095 K⁻¹ and M_S=5.39 μg h⁻¹ m⁻².The detected carbonyl compound concentrations were unexpectedly high (maximum formaldehyde concentration was 18.1 ppbv and 3.4 ppbv for butyraldehyde) for an open field. Possible reasons for these concentrations are the combination of primary emission from the plants induced by high temperature and high ozone stress, the secondary formation from biogenically and advected anthropogenically emitted VOC at high radiation intensities and furthered by the low wind speeds at this time.     

Cereal waste burning pollution observed in the town of Vitoria (northern Spain)

Agricultural waste burning is a widespread practice throughout the world but there is little information about its pollutant impact. This paper deals with a preliminary study of the pollution observed in Vitoria (Northern Spain) caused by cereal waste burning. The mean hourly flux of pollutants produced by cereal waste burning fires can reach values of 1.4 kt of CO₂, 13 t of TPM and 3 t of NO_x in the area around Vitoria. Measurements obtained in the area of emission and inside fire plumes show high ratios (NO₂/NO_x) indicating that nitrogen oxides emitted by the source undergo a rapid transformation in the same area of emission. Results relating to aerosol composition collected in Vitoria during burning periods show an increase in the concentration of K⁺, NO₃⁻ and Cl⁻ ions, that are inter-correlated. The modification of the ionic composition of aerosols also affects the chemistry of the rain collected in Vitoria. During the burning period, it is particularly noticeable that anthropogenic pollution (usually identifiable by the correlation between SO₄²⁻ and NO₃⁻ concentrations) disappears, indicating the existence of an independent source of NO₃⁻ not linked to the SO₄²⁻ source. Similar results were deduced studying BAPMON data collected in Spain during cereal waste burning. Finally, we note that ozone concentration measured at Vitoria is not affected by the pollution generated by the burning fires.     

Analysis of the effects of combustion emissions and Santa Ana winds on ambient ozone during the October 2007 southern California wildfires

Combustion emissions and strong Santa Ana winds had pronounced effects on patterns and levels of ambient ozone (O₃) in southern California during the extensive wildland fires of October 2007. These changes are described in detail for a rural receptor site, the Santa Margarita Ecological Reserve, located among large fires in San Diego and Orange counties. In addition, O₃ changes are also described for several other air quality monitoring sites in the general area of the fires. During the first phase of the fires, strong, dry and hot northeasterly Santa Ana winds brought into the area clean continental air masses, which resulted in minimal diurnal O₃ fluctuations and a 72-h average concentration of 36.8 ppb. During the second phase of the fires, without Santa Ana winds present and air filled with smoke, daytime O₃ concentrations steadily increased and reached 95.2 ppb while the lowest nighttime levels returned to ～0 ppb. During that period the 8-h daytime average O₃ concentration reached 78.3 ppb, which exceeded the federal standard of 75 ppb. After six days of fires, O₃ diurnal concentrations returned to pre-fire patterns and levels.     

Ozone, nitric acid, and ammonia air pollution is unhealthy for people and ecosystems in southern Sierra Nevada, California

Two-week average concentrations of ozone (O₃), nitric acid vapor (HNO₃) and ammonia (NH₃) were measured with passive samplers during the 2002 summer season across the central Sierra Nevada Mountains, California, along the San Joaquin River drainage. Elevated concentrations of the pollutants were determined with seasonal means for individual sites ranging between 62 and 88 ppb for O₃, 1.0-3.8 μg m⁻³ for HNO₃, and 2.6-5.2 μg m⁻³ for NH₃. Calculated O₃ exposure indices were very high, reaching SUM00-191 ppm h, SUM60-151 ppm h, and W126-124 ppm h. Calculated nitrogen (N) dry deposition ranged from 1.4 to 15 kg N ha⁻¹ for maximum values, and 0.4-8 kg N ha⁻¹ for minimum values; potentially exceeding Critical Loads (CL) for nutritional N. The U.S., California, and European 8 h O₃ human health standards were exceeded during 104, 108, and 114 days respectively, indicating high risk to humans from ambient O₃.     

Tropical tropospheric ozone observed in Thailand

The mixing ratios of surface ozone at two rural/remote sites in Thailand, Inthanon and Srinakarin, have been measured continuously for the first time. Almost identical seasonal variations of O₃ with dry season maximum and a wet season minimum with a large seasonal amplitude are observed at both sites during 1996–1998. At Inthanon, the monthly averaged O₃ mixing ratios range 9–55 ppb, with the annual average of 27 ppb. The ozone mixing ratios at Srinakarin are in the similar range, 9–45 ppb with annual average of 28 ppb. Based on trajectory analysis of O₃ data at Inthanon, the long-range transport of O₃ under Asian monsoon regime could primarily explain the low O₃ mixing ratios of 13 ppb in clean marine air mass from Indian Ocean during wet season but only partly explain the relatively low O₃ mixing ratios, 26 ppb or less, in continental air mass from northeast Asia either in wet or dry season. The highest O₃ mixing ratios are found in air masses transported within southeast Asia, averaged 46 ppb in dry season. The high O₃ mixing ratios during the dry season are suggested to be significantly due to the local/sub-regional scale O₃ production triggered by biomass burning in southeast Asia rather than long-range transport effect.     

Characterizations of chemical oxidants in Mexico City: A regional chemical dynamical model (WRF-Chem) study

The formation of chemical oxidants, particularly ozone, in Mexico City were studied using a newly developed regional chemical/dynamical model (WRF-Chem). The magnitude and timing of simulated diurnal cycles of ozone (O₃), carbon monoxide (CO) and nitrogen oxides (NO_x)_, and the maximum and minimum O₃ concentrations are generally consistent with surface measurements. Our analysis shows that the strong diurnal cycle in O₃ is mainly attributable to photochemical variations, while diurnal cycles of CO and NO_x mainly result from variations of emissions and boundary layer height. In a sensitivity study, oxidation reactions of aromatic hydrocarbons (HCs) and alkenes yield highest peak O₃ production rates (20 and 18 ppbv h⁻¹, respectively). Alkene oxidations, which are generally faster, dominate in early morning. By late morning, alkene concentrations drop, and oxidations of aromatics dominate, with lesser contributions from alkanes and CO. The sensitivity of O₃ concentrations to NO_x and HC emissions was assessed. Our results show that daytime O₃ production is HC-limited in the Mexico City metropolitan area, so that increases in HC emissions increase O₃ chemical production, while increases in NO_x emissions decrease O₃ concentrations. However, increases in both NO_x and HC emissions yield even greater O₃ increases than increases in HCs alone. Uncertainties in HC emissions estimates give large uncertainties in calculated daytime O₃, while NO_x emissions uncertainties are less influential. However, NO_x emissions are important in controlling O₃ at night.     

Results from a pilot-scale air quality study in Addis Ababa, Ethiopia

Twenty-one samples were collected during the dry season (26 January–28 February 2004) at 12 sites in and around Addis Ababa, Ethiopia and analyzed for particulate matter with aerodynamic diameter <10 μm (PM₁₀) mass and composition. Teflon-membrane filters were analyzed for PM₁₀ mass and concentrations of 40 elements. Quartz-fiber filters were analyzed for chloride, sulfate, nitrate, and ammonium ions as well as elemental carbon (EC) and organic carbon (OC) content. Measured 24-h PM₁₀ mass concentrations were <100 and 40 μg m⁻³ at urban and suburban sites, respectively. PM₁₀ lead concentrations were <0.1 μg m⁻³ for all samples collected, an important finding because the government of Ethiopia had stopped the distribution of leaded gasoline a few months prior to this study. Mass concentrations reconstructed from chemical composition indicated that 34–66% of the PM₁₀ mass was due to geologically derived material, probably owing to the widespread presence of unpaved roads and road shoulders. At urban sites, EC and OC compounds contributed between 31% and 60% of the measured PM₁₀ while at suburban sites carbon compounds contributed between 24% and 26%. Secondary sulfate aerosols were responsible for <10% of the reconstructed mass in urban areas but as much as 15% in suburban sites, where PM₁₀ mass concentrations were lower. Non-volatile particulate nitrate, a lower limit for atmospheric nitrate, constituted <5% and 7% of PM₁₀ at the urban and suburban sites, respectively. At seven of the 12 sites, real-time PM₁₀ mass, real-time carbon monoxide (CO), and instantaneous ozone (O₃) concentrations were measured with portable nephelometers, electrochemical analyzers, and indicator test sticks, respectively. Both PM₁₀ and CO concentrations exhibited daily maxima around 7:00 and secondary peaks in the late afternoon and evening, suggesting that those pollutants were emitted during periods associated with motor-vehicle traffic, food preparation, and heating of homes. The morning concentration maxima were likely accentuated by stable atmospheric conditions associated with overnight surface temperature inversions. Ozone concentrations were measured near mid-day on filter sample collection days and were in all cases <45 parts per billion.     

Smoke emissions from biomass burning in a Mediterranean shrubland

Gaseous and particulate samples from the smoke from prescribed burnings of a shrub-dominated forest with some pine trees in Lousã Mountain, Portugal, in May 2008, have been collected. From the gas phase Fourier transform infrared (FTIR) measurements, an average modified combustion efficiency of 0.99 was obtained, suggesting a very strong predominance of flaming combustion. Gaseous compounds whose emissions are promoted in fresh plumes and during the flaming burning phase, such as CO₂, acetylene and propene, produced emission factors higher than those proposed for savannah and tropical forest fires. Emission factors of species that are favoured by the smouldering phase (e.g. CO and CH₄) were below the values reported in the literature for biomass burning in other ecosystems. The chemical composition of fine (PM_2.5) and coarse (PM_2.5–10) particles was achieved using ion chromatography (water-soluble ions), instrumental neutron activation analysis (trace elements) and a thermal–optical transmission technique (organic carbon and elemental carbon). Approximately 50% of the particulate mass was carbonaceous in nature with a clear dominance of organic carbon. The organic carbon-to-elemental carbon ratios up to 300, or even higher, measured in the present study largely exceeded those reported for fires in savannah and tropical forests. More than 30 trace elements and ions have been determined in smoke aerosols, representing in total an average contribution of about 7% to the PM₁₀ mass.